WO2001014060A2 - Compositions catalytiques a surface limitee - Google Patents

Compositions catalytiques a surface limitee Download PDF

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Publication number
WO2001014060A2
WO2001014060A2 PCT/US2000/040744 US0040744W WO0114060A2 WO 2001014060 A2 WO2001014060 A2 WO 2001014060A2 US 0040744 W US0040744 W US 0040744W WO 0114060 A2 WO0114060 A2 WO 0114060A2
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Prior art keywords
article
catalyst
mesoporous
immobilized
ligand
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WO2001014060A3 (fr
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Jackie Y. Ying
Christian P. Mehnert
John S. Lettow
Dejian Huang
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Massachusetts Institute of Technology
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Massachusetts Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2286—Alkynes, e.g. acetylides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
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    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution

Definitions

  • the present invention relates to novel ultra-large porous compositions, and organometallic catalysts immobilized on these compositions, including asymmetric organometallic catalysts. Reactions performed by these catalysts include hydrogenation, hydroformylation, carbonylation, carbon-carbon coupling reactions, as well as asymmetric reactions such as asymmetric hydrogenation.
  • the homogeneous catalysts show good activity and can be tailored to allow for a high degree of product selectivity.
  • heterogeneous catalysts do not afford comparable performance, these catalysts offer other advantages such as ease of catalyst recovery.
  • a number of different techniques have been developed to "heterogenize" homogeneous transition metal catalysts for various catalytic reactions. These techniques involve (i) dissolution of modified homogeneous catalysts in a liquid phase which is not miscible with the reaction solvent, and subsequent support of the non-soluble phase on solid particles, or (ii) covalent linkage of catalyst molecules to silica beads and polymer matrices.
  • These methods result in low surface area catalysts that have only a small fraction of active component exposed to the reaction mixture.
  • One aspect of the present invention provides an article comprising an organometallic catalyst immobilized on a polymer-templated composition having at least about 50% of a total pore volume comprising pores with a mean diameter of at least about 50 A.
  • Another aspect of the present invention provides an article comprising an asymmetric organometallic catalysts immobilized on a surface via an achiral ligand.
  • a method comprises forming a mesoporous composition via a polymer template, the mesoporous composition having at least about 50% of a total pore volume comprising pores with a mean diameter of at least about 50 A.
  • the method also comprises immobilizing an organometallic catalysts on the mesoporous composition.
  • Another aspect of the present invention provides a method for performing a catalytic reaction.
  • the method comprises contacting a catalyst with a substrate.
  • the catalyst comprises an organometallic complex immobilized on a mesoporous composition having at least about 50% of a total pore volume comprising pores with a mean diameter of at least about 50 A.
  • Another aspect of the present invention provides an article comprising a polymerization catalyst immobilized on a porous composition.
  • the composition has pores of a predetermined mean diameter to define a molecular weight distribution of a polymer.
  • Another aspect of the present invention provides an article comprising catalyst immobilized on a porous composition.
  • the composition has pores of a predetermined mean diameter to influence stereoselectivity.
  • Another aspect of the present invention provides a system comprising a plurality of supports. Each support comprises a composition having pores of a mean diameter of at least about 50 A.
  • FIG. 1 shows a scheme for covalent immobilization of an organometallic catalyst, 1, to a portion of a mesoporous composition
  • FIG. 2 shows a scheme for covalent immobilization of an organometallic catalyst, 2, to a portion of a mesoporous composition
  • FIG. 3 shows a scheme for covalent immobilization of an organometallic catalyst, 3, to a portion of a mesoporous composition
  • FIG. 4 shows a scheme for immobilizing an organometallic catalyst to a portion of mesoporous composition by reacting the mesoporous composition with a ligand capable of complexing an organometallic catalyst;
  • FIG. 5 shows a scheme for immobilizing two adjacent ligands on a portion of a mesoporous composition in which the two adjacent ligands complex one metal center;
  • FIG. 6 shows a scheme for ionic immobilization of a metal center [M*]
  • FIG. 7 shows a scheme for immobilizing an organometallic catalyst, [M*], via an isocyanide linkage
  • FIG. 8 shows a scheme for immobilizing an organometallic catalyst by providing a catalyst, 14, having a ligand reactive with a mesoporous composition
  • FIG. 9 shows photoacoustic infrared spectra of (a) a homogenous ruthenium catalyst, (b) the mesoporous material before immobilization of the ruthenium catalyst, (c) after immobilization of the ruthenium catalyst, and (d) after immobilization and a methanol rinse;
  • FIG. 10 shows a scheme for immobilization of an asymmetric organometallic catalyst via reaction of a reactive ligand on the catalyst with the mesoporous composition
  • FIG. 11 shows a plot of number of moles cyclohexane produced per mole of rhodium (y-axis) vs. time (x-axis) via hydrogenation of cyclohexene by a rhodium organometallic catalyst immobilized on mesoporous silica foam;
  • FIG. 12 shows a plot of conversion of methyl-2-acetamidoacrylate (y-axis) vs. time (x-axis) via hydrogenation with an immobilized organometallic catalyst, demonstrating that immobilized organometallic catalysts of the present invention can be reused without significant loss of activity or selectivity;
  • FIG. 13 shows a plot comparing conversion of methyl-2-acetamidoacrylate (y-axis) vs. time (x-axis) between the immobilized organometallic catalyst vs. the homogenous catalyst;
  • FIG. 14 shows a plot of conversion of dimethylitaconate (y-axis) vs. time (x-axis) via hydrogenation with an immobilized organometallic catalyst
  • FIG. 15 shows a plot of conversion of methyl-2 acetamidoacrylate (y-axis) vs. time via hydrogenation with an immobilized organometallic catalyst.
  • the present invention relates to a catalytic system comprising a catalyst immobilized on novel porous support materials. Typical previous porous support materials contain a substantial number of micropores, which, upon immobilizing a catalyst therein, can result in clogging due to the small size of these pores.
  • the present invention relates, in part, to the discovery of materials having ultra-large pores, and the discovery that undesired effects such as clogging are substantially prevented, resulting in a significantly increased catalytic activity, with ultra-large pores. It is believed that catalytic activity is significantly enhanced when catalytic sites are situated within pores of a large diameter.
  • one aspect of the present invention provides an article comprising an organometallic catalyst immobilized on a polymer-templated mesoporous composition.
  • Polymer-templated refers to a process for making porous materials via the use of polymer microparticles or block co-polymers which can act as a template to control pore size during condensation of inorganic reactants.
  • mesoporous materials prepared by amphiphilic block copolymers which have mesostructural ordering properties.
  • a “mesoporous composition” refers to a porous solid having pores of a mean diameter of at least about 20 A and no more than about 1 ⁇ m.
  • Mesoporous diameter refers to the mean of all the pore diameters in the composition.
  • An advantageous feature of the present invention is that a large percentage of pores in the composition have large diameters ("ultra-large pores").
  • Many prior art porous materials afford high surface areas by providing numerous pores having mean diameters of 10 A, or even less.
  • organometallic catalysts can have a dimension ranging from approximately 10 A to 30 A (of course the size can vary from this range depending on the metal and ligands involved), and immobilization of such catalysts in a pore having a diameter of at least about 50 A provides sufficient space to allow the catalyst to provide its maximal activity.
  • the pores of the mesoporous composition have a mean diameter of at least 50 A, more preferably at least about 60 A, more preferably at least about 100 A, more preferably at least about 150 A, more preferably at least about 200 A, even more preferably at least about 250 A, and even more preferably still at least about 300 A.
  • the materials of the present invention can be distinguished from such prior art porous materials which comprise a majority of small pore sizes and only a few large pore sizes which "artificially" increase the mean pore diameter.
  • at least about 50% of more preferably at least about 60%, more preferably at least about 70%, and even more preferably at least about 80% a total pore volume comprises pores with a mean diameter of at least about 50 A, or any of the higher dimensions as defined previously.
  • the present invention encompasses various combinations of pore diameters and percentages of pores having particular diameters.
  • At least about 50% of the total pore volume comprises pores with a mean diameter of at least about 50 A or higher
  • other materials can have at least 60%, 70% or even 80% of the total pore volume comprising pores with a mean diameter of at least about 50 A or higher.
  • Materials of the invention having ultra-large pores also generally feature high surface areas.
  • High surface areas allow a large concentration of catalysts to be immobilized on the surface. This provides porous materials with very high catalytic activity. Other advantages of high catalyst concentrations are a lower volume of porous materials required, which is useful for reactors with a limited volume. In addition, contact time and residence time is reduced.
  • High surface areas also allow catalytically active sites to be separated, preventing dimerization of catalysts, or other undesired recombination effects. "Dimerization" can result in a combination of at least two active sites which results in modification of the catalyst, possible loss of catalytic activity and thus, deactivation of the catalyst.
  • the composition has a surface area of at least about 500 m 2 /g, more preferably about 600 m /g, and even more preferably at least about 700 m /g.
  • Such high surface areas can form as a result of large pore volumes, such as a total pore volume (sum of volumes of all the pores in the material per unit weight) of at least about 0.5 cmVg, more preferably at least about 0.6 cm /g, more preferably at least about 0.7 cm /g, more preferably at least about 0.8 cm 3 /g, more preferably at least about 0.9 cm 3 /g, more preferably at least about 1.0 cm 3 /g, more preferably at least about 1.1 c Vg, more preferably at least about 1.2 cm /g, more preferably at least about 1.3 cm /g, and more preferably still at least about 1.4 cm /g.
  • High pore volumes provide a foam material and when coupled with high surface areas and large pore sizes, such foams advantageously optimize conditions for catalytic reactions. For example, diffusion of substrates into the pores to access the catalytically active sites is facilitated, as well as diffusion of products out of the porous materials, with minimal steric hindrance.
  • the composition can be crystalline, amorphous, or a combination of such features.
  • the composition can have short-range order to afford an x-ray diffraction pattern, yet feature amorphous pore walls.
  • the mesoporous composition is a ceramic.
  • ceramics include carbides, suicides, nitrides and oxides.
  • the ceramic is an oxide such as a silicate, i.e., includes SiO 2 units.
  • silicates that can be used in the present invention include SBF-15 and mesoporous silica foam (MCF). It is a feature of certain embodiments of the present invention that the organometallic catalysts can be immobilized directly to the silicate without the incorporation of a dopant metal atom into the mesoporous composition.
  • the ceramic further includes a dopant metal ion.
  • Dopant metal ions can allow tailoring of the pore size, pore shape, overall charge balance of the composition (i.e. presence and/or number of counterions are influenced by the specific dopant ion used).
  • dopant ions can immobilize organometallic metallic complexes by coordinating to ligands having an atom capable of donating a lone pair of electrons.
  • dopant metal ions includes main group metals such as aluminum and boron, transition metals such as niobium, tantalum, titanium and zirconium, and lanthanides and actinides.
  • Organic metal catalyst refers to an inorganic metal complex capable of catalyzing a reaction, typically comprising at least one central metal atom bonded to at least one ligand.
  • the organometallic catalyst includes a metal, such as a transition metal or a lanthanide.
  • transition metals include ruthenium, rhodium, iridium, palladium, platinum, osmium, iron, cobalt, nickel, molybdenum, tungsten, copper, gold, silver, zirconium, titanium and hafnium.
  • Other examples of metals in organometallic catalysts include uranium.
  • the organometallic catalyst includes a ligand that is immobilized on the mesporous composition. "Immobilized” refers to a chemical interaction between the catalyst and the mesoporous composition, as opposed to physical immobilization, e.g. adsorption or trapping within a glassy matrix.
  • the catalyst can be covalently immobilized on the porous composition preferably by formation of a covalent bond between the ligand and the mesoporous composition. The covalent bond can be relatively non-polar, i.e.
  • the bonding electrons are relatively localized in the region of the two nuclei sharing the bond.
  • Such covalent bonding typically occurs between two organic substituents or mean group heteroatoms such as silicon, nitrogen, oxygen, phosphorous, sulfur, etc.
  • a covalent bond can involve coordination of an atom having a lone electron pair donated to a metal atom.
  • this method of immobilization allows facile tailoring of the other ligands to optimize catalytic activity and selectivity.
  • ligands capable of covalent immobilization to the mesoporous composition include: an amine, a phosphine, an amide, an imine, an amido, a thiol, a thiolate an alkyl, an aryl, an arene, a cyclopentadienyl, an alkoxide, a phosphide, a phosphite, a nitrile, an isonitrile and a sulfonate ligand.
  • the ligand can be monodentate or multi-dentate (e.g., bidentate, tridentate, a porphyrin, a crown ether, a cryptand, etc.).
  • more than one ligand can immobilize a catalyst.
  • These ligands can be the same or can involve a combination of different ligands.
  • Another advantageous feature of the present invention provides an organometallic catalyst immobilized on the porous composition which is capable of being well-defined. Previously, due to the nature of ceramics having many possible sites for adsorbing catalysts, the adsorbed catalyst was not easily characterizable, and thus not well-defined. By providing ligands having well-known bonding modes with inorganic complexes (i.e. known by characterization of analogous inorganic complexes in solution), a structure of the resulting immobilized organometallic complex can be controlled.
  • the organometallic catalyst is capable of being characterized by a number of techniques, such as x-ray diffraction, NMR, IR, elemental analysis, UV-vis, TGA, differential scanning calorimetry, nitrogen adsorption analysis for surface area analysis and chemisorption analysis for metal analysis.
  • x-ray diffraction NMR, IR, elemental analysis, UV-vis, TGA, differential scanning calorimetry, nitrogen adsorption analysis for surface area analysis and chemisorption analysis for metal analysis.
  • FIG. 4 shows a schematic of a portion of a surface of a mesoporous composition (a silicate, as represented by the SiO 2 standard) covalently bonded to a ligand.
  • Species 4 of FIG. 4 comprises a covalent bond formed between a silicon atom of the mesoporous composition and a carbon atom of an amine ligand.
  • the amine ligand of species 4 can in itself be used to bond to an organometallic complex in a coordinative fashion. Alternatively, the amine ligand can be further derivatized with phosphine ligands, as shown in species 5.
  • phosphine ligands are excellent candidates for ligating transition metals, such as palladium as shown in species 6.
  • Species 6 includes a bidentate ligand, i.e. the diphosphine ligand, which can complex a Pd(CH 3 ) group.
  • FIG. 5 shows an example of immobilizing a metal complex via two separate ligands and a scheme for appending a single phosphine ligand to a portion of a silicate surface.
  • Reaction of the hydroxy groups presented by the silicate surface with a triethoxysilane having a phosphine group, (or any other organic fragment capable of reacting with hydroxy groups to ultimately form a covalent bond) results in the formation of a monophosphine fragment immobilized on the silicate surface, as shown in species 7.
  • species 7 shows an example of immobilizing a metal complex via two separate ligands and a scheme for appending a single phosphine ligand to a portion of a silicate surface.
  • the organometallic catalyst can be ionically immobilized on the mesoporous composition, preferably having pores of a mean diameter of at least about 50 A, and other dimensions and pore volume percentages as defined previously.
  • An "ionically immobilized catalyst” involves an inorganic complex having a particular charge that is bound to a site on the composition having an opposite charge.
  • the site can comprise a single charged atom (i.e. a cation or an anion), or at least one charge (+1 or -1 or greater, i.e. +2, -2, etc.) delocalized over a group of atoms. This type of immobilization is distinguished from mere adsorption between neutral species that are partially charged.
  • ionic immobilization is achieved by ion exchange.
  • the support material prior to ion exchange can have a negative charge counterbalanced by positively charged ions such as metal ions.
  • these metal ions are alkaline, alkaline earth, or main group metal ions including nitrogen-, sulfur-, phosphorus-based ions (e.g. quaternary ammonium ions, phosphonium ions, sulfonate, etc.). Exposure of this ionic species to a cationic complex can result in ion-exchange of the cationic complex for the positively charged metal ion. This method of immobilization can be achieved for almost any cationic complex.
  • ionically immobilized catalyst resembles the ionic molecular species in solution.
  • the catalyst maintains the same high activity as its homogeneous solution counterpart, while providing ease of recovery from the reaction mixture.
  • FIG. 6 An example of ion-exchange is illustrated in FIG. 6.
  • the protons in surface-bound hydroxy groups can be exchanged for lithium ions, or other analogous ions as described previously.
  • cationic metal complexes such as 1 la and 1 lb can be ionically immobilized by exchanging the lithium ions for cationic metal complexes [M*].
  • the ionically immobilized catalyst is an anionic complex.
  • the reverse situation exists where an anionic complex ion-exchanges with an anion in the composition.
  • catalytic reactions involve hydrogenation, hydroboration, hydrosilylation, hydroformylation, hydrocyanation, epoxidation, carbon-carbon coupling, carbon-nitrogen coupling, polymerization, ring-closing/opening metathesis of olefins and carbonylation.
  • carbon-carbon coupling reactions are the Heck reaction and Suzuki coupling.
  • the palladium complex of species 6 in FIG. 4 is an example of a catalyst for a Heck carbon-carbon coupling reaction.
  • an article comprising an organometallic catalyst for catalyzing an asymmetric reaction.
  • An "asymmetric reaction” refers to a stereoselective reaction in which a reactant, either provided as a prochiral molecule, a racemic mixture or as a pure enantiomer, is converted to a product in a stereoselective manner.
  • asymmetric catalysts of the invention provide sufficient stereoselectivity such that an enantiomeric excess of at least about 50% is achieved.
  • the enantiomeric excess is at least about 60%, more preferably at least about 70%, more preferably at least about 80%, even more preferably at least about 95%, and more preferably still at least about 99%.
  • Examples of asymmetric reactions include reduction of unsaturated substrates and carbon-carbon bond forming reactions.
  • Examples of such reactions include hydrogenation, hydroboration, hydrosilylation, hydroformylation, hydrocyanation, epoxidation, carbon-carbon coupling, carbon-nitrogen coupling, polymerization, ring-closing/opening metathesis of olefins and carbonylation.
  • an "asymmetric catalyst” refers to a catalyst capable of catalyzing an asymmetric reaction.
  • an asymmetric catalyst is chiral, as provided by chiral ligands.
  • An advantageous feature of the asymmetric catalyst of the present invention provides immobilization of the asymmetric catalyst to a surface via an achiral ligand.
  • prior art asymmetric catalysts immobilized on solid surfaces involved immobilization through the chiral ligands.
  • the chiral ligand is the most expensive portion of the asymmetric catalyst and functionalizing this ligand to allow immobilization to a surface increases catalyst can be costly.
  • each new chiral ligand will require functionalization for immobilization on the surface.
  • the present invention advantageously features immobilization through an achiral ligand which is generally inexpensive in relation to the chiral ligand, and/or easier to modify.
  • the chiral ligand is free of direct-bonding to a surface, and facile substitution of the chiral ligand can occur for screening purposes.
  • Strong achiral ligands include: an amine, a phosphine, an amide, an imine, an amido, a thiol, a thiolate an alkyl, an aryl, an arene, a cyclopentadienyl and its derivatives, an alkoxide, a phosphide, a phosphite, a nitrile, an isonitrile and a sulfonate ligand.
  • the surface comprises a mesoporous composition having large pore sizes as described previously and percentages of large pore sizes as described previously.
  • FIG. 1 shows a schematic of a catalytic composition represented by compound 1; n represents an integer from 0 to 12; L represents at least one achiral ligand capable of immobilization to a surface; M represents a transition metal, which may be charged or neutral; L* represents a chiral ligand; L' represents auxiliary ligands that help to stabilize the metal complexes, such ligands include, but are not limited to, ether, water, olefin, alkyl or hydrogen radical; and -O-Si-O-Si-O- represents a portion of a silicate surface.
  • One example of an article of the present invention includes asymmetric organometallic catalyst 2 (FIG.
  • the chiral ligand is a chiral bidentate phosphine ligand, preferably BINAP.
  • the metal ruthenium is linked to the surface of the silica through an isocyanide group an L' represents at least one auxiliary ligand.
  • Compound 3 represents another example of an article of the present invention.
  • the asymmetric organometallic catalyst is immobilized to the silica surface through an ⁇ -coordination with an arene.
  • the catalyst does not suffer from severe electronic or steric modifications and the catalytic activity of the catalyst is preserved. This allows screening of the molecular catalyst prior to immobilization by using stand solution-type methods.
  • Optimal catalysts can be chosen for immobilization.
  • the catalyst is "directly immobilized" on the mesoporous composition, i.e. there are no extra linker atoms intervening between the parent molecular catalyst and the mesoporous composition. Direct immobilization can occur covalently or ionically. It is readily understood that in some instances, linker atoms may be necessary.
  • the catalyst of the present invention can be used as a catalyst in asymmetric hydrogenation of olefins such as, 2-(6-methoxy-2naphthyl)propenoic acid and its methyl ester, ⁇ and ⁇ -valerolactone, ⁇ -(N-acetylamino)methylacrylate, as well as compounds such as dimethyl itaconate.
  • olefins such as, 2-(6-methoxy-2naphthyl)propenoic acid and its methyl ester, ⁇ and ⁇ -valerolactone, ⁇ -(N-acetylamino)methylacrylate, as well as compounds such as dimethyl itaconate.
  • the article can be recovered by simple filtration or centrifugation and reused for subsequent catalysis runs without significant loss of activity.
  • the article can also be used as catalysts in hydrogenation of acetophenone using isopropanol as hydrogen donor and solvent.
  • a method involves forming a mesoporous composition via a polymer template, i.e. a polymer- templated mesoporous composition.
  • the mesoporous composition has at least about 50% of a total pore volume comprising pores with a mean diameter of at least about 50 A, or other dimensions and percentages as described previously.
  • the method also comprises immobilizing an organometallic catalyst on the mesoporous composition.
  • the immobilization can be covalent or ionic. Where the immobilization is covalent, the method can involve providing a ligand having a first site capable of bonding to a metal and a second site reactive with the mesoporous composition.
  • the ligand is then immobilized to the mesoporous composition via the second site.
  • the ligand comprises a first site reactive with the mesoporous composition, i.e. a triethoxysilyl group.
  • the triethoxysilyl group can react with hydroxyl groups inherent in the mesoporous composition via condensation reaction.
  • the ligand also comprises a first site capable of bonding to a metal, i.e. a diphenylphosphino group.
  • the step of immobilizing further comprises bonding a metal to the ligand via the first site. Referring back to FIG.
  • the step of immobilizing comprises providing the organometallic catalyst having a ligand reactive with a mesoporous composition and immobilizing the organometallic catalyst on the mesoporous composition via the reactive ligand.
  • FIG. 8 An example of this embodiment is illustrated in FIG. 8. In FIG. 8.
  • the asymmetric organometallic catalyst includes an acetonitrile ligand which can be substituted by an isonitrile group containing a triethoxysilyl group, resulting in a ruthenium isonitrile complex as shown in species 14, in which the isonitrile ligand comprises a triethoxysilyl group reactive with a surface, such as surface-bond hydroxy groups of a silicate. Reaction of species 14 with the silicate results in species 15 in which the metal complex is bound to the silicate via the isonitrile-silyl group linkage.
  • the step of immobilizing comprises ionically immobilizing the organometallic catalyst on the mesoporous composition.
  • An example of such immobilization is shown in FIG. 6, which was described previously.
  • FIG. 6 involves exchanging protons present on a surface with a cation, such as an alkaline cation or alkaline earth cation.
  • the cation can then be ion-exchanged with a cationic metal complex [M*].
  • the metal complex can include a ligand having a group capable of ion exchanging directly with the protons of a surface-bound hydroxy group.
  • Another aspect of the present invention provides a method for performing a catalytic reaction.
  • the method involves contacting a catalyst with a substrate in which the catalyst comprises an organometallic complex immobilized on a mesoporous composition having at least about 50% of a total pore volume comprising pores with a mean diameter of at least about 50 A.
  • the mean diameter can be greater than 50 A as discussed previously and the percentages of the total of pore volume can also have previously recited values.
  • the catalytic reaction can occur in a solution/slurry phase. Alternatively, the reaction can occur in the gas phase.
  • the reaction is a heterogeneous type reaction in which a catalyst can be recovered by filtration or centrifugation and reused for subsequent reactions.
  • the activity of the catalyst is substantially maintained during subsequent reactions.
  • the catalytic reaction is a asymmetric reaction.
  • a substrate in one or more of these embodiments, more than one substrate and/or a substrate and other reactants may be required.
  • a substrate in a hydrogenation reaction, can be an unsaturated species such as an olefin. Hydrogenation occurs where the olefin chemically reacts with the catalysts and is reduced to a more saturated species by the addition of a reactant such as hydrogen gas.
  • a reactant such as hydrogen gas.
  • An example of a reaction involving two substrates are carbon- carbon coupling reactions.
  • organometallic complexes immobilized on porous surfaces having previously defined dimensions palladium complexes (e.g. see species 6 of FIG. 4), rhodium complexes (e.g. see, for example, species 8 of FIG. 5 and species 11a and 1 lb of FIG. 6) and ruthenium phosphine complexes (e.g. see, for example, species 13 of FIG. 7) have been immobilized on the surface of mesoporous materials by a number of different methods.
  • Catalytically active complexes have been bound to mesoporous supports by condensing alkoxysilanes modified with amine, phosphine, or isonitrile groups to the surface of the mesopores in processes similar to those described for the immobilization of palladium complexes.
  • the ion-exchange of cationic organometallic compounds onto the anionic surfaces of modified mesoporous silicates, such as aluminum-doped silicates or [BF ]- modif ⁇ ed silicates is also an effective means of immobilizing a wide range of compounds onto mesoporous materials. And lastly strong niobium-nitrogen bonds can be used to anchor amine-containing organometallic complexes to niobium-doped silicate surfaces.
  • the composition has pores of a predetermined mean diameter to influence stereoselectivity.
  • a predetermined pore size such that the pores dictate a particular orientation of the catalyst and substrate orientation, resulting in high stereoselectivity.
  • Another aspect of the present invention provides an article comprising a polymerization catalyst.
  • the polymerization catalyst is immobilized on a porous composition where the composition has pores of a predetermined mean diameter to define a molecular weight distribution of a polymer. This aspect provides a novel method for obtaining polymers with relatively low polydispersity values.
  • Polymer growth is limited to the size of the pores, i.e., upon formation of a polymer that completely occupies a pore, monomers can no longer enter into the pore and polymerization ceases.
  • Typical polymerization catalyst involves carbon-carbon coupling, carbon-nitrogen coupling, ring opening metathesis and other coupling reactions.
  • porous materials that can be used for combinatorial chemistry.
  • a support material is typically used to bind at least one reactant or catalyst. The reactant is then exposed to a variety of other reactants.
  • a combinatorial library can be achieved by providing a plurality of support materials, for example provided as beads, where each bead is bound to the same reagent. Each bead containing the reagent is then exposed to a unique second reagent such that a different chemical reaction occurs on each different bead. Typically, the first reagent is supported on a surface of the bead.
  • porous support materials can increase the extent of reaction on a bead due to the high surface area provided by the support material. Advantages of using porous supports include high catalytic concentration resulting in high catalytic activity and high yields.
  • Example 1 Fabrication of Mesoporous Supports This example outlines the synthesis of porous materials having large pore sizes. SBA-15 and mesoporous silica foam (MCF) materials have been prepared in a similar manner to the published literature (SBA-15: D. Zhao, et al, Science, 1998, vol. 279, pp. 548- 552; MCF: P. Schmidt- Winkel, Journal of the American Chemical Society, 1999, vol. 121, pp. 254-255).
  • TEOS Tetraethylorthosilicate
  • SBA-15 mesoporous materials are formed.
  • SBA-15 consists of a hexagonally-packed array of cylindrical pores with median pore diameters of 60-100 A. The material gives distinct small- angle X-ray scattering (SAXS) peaks with d-spacings of (100) 104 A, (110) 59 A, (200) 51 A.
  • the BET surface area of SBA-15 is typically in excess of 900 m 2 /g.
  • MCF are formed.
  • the mesoporous foam materials have median pore diameters of 150-350 A and surface areas in excess of 700 m 2 /g.
  • SBA-15 consists of a hexagonal array of long, straight cylindrically shaped pores Surface area: > 700 m /g
  • Pore size distribution 80% of pores within ⁇ 10 A (as determined by fraction of total pore volume, i.e. volume of pores with median diameter ⁇ 10 A / total pore volume)
  • Pore volume > 0.6 cm /g Porosity: > 50% (i.e. void fraction > 0.5)
  • Constriction factor (defined as the ratio of the widest diameter of the pore to the narrowest diameter of the pore): ⁇ 2 Mesoporous Silica Foam: consists of spherical pores interconnected by small windows, the spherical pores need not be packed in any specific arrangement .
  • Pore size distribution 80% of pores within ⁇ 100 A of the median pore diameter Pore volume: > 1.4 cm 3 /g Porosity: > 75% Constriction factor: 1-5
  • Degassed mesoporous silicate-based SBA-15 material was treated with 3-aminopropyltriethoxysilane to initiate the condensation reaction between surface- bound hydroxy groups and the ethoxysilane fragments, forming the surface immobilized aminopropyl complex 4 in FIG. 4. This was accomplished by suspending the mesoporous material in a solution of 3-aminopropyltriethoxysilane in ⁇ -heptane and refluxing for 12 h.
  • the resulting material, Pd-TMS 12 c retained its hexagonally-packed porous structure as shown by SAXS.
  • Transmission electron microscopy (TEM) confirmed the hexagonally- packed structure of the large pores in Pd-TMS 12°.
  • the BET surface area of Pd-TMS 12 c was 161 m 2 /g, which was less than that found for the untreated SBA-15 material (994 m 2 /g).
  • the BJH (Brunauer-Joyner-Halenda) pore size distribution of Pd-TMS 12° exhibited a narrow peak centered at 40.0 A, which was smaller than for SBA-15 (70.5 A).
  • rhodium and ruthenium phosphine complexes have been immobilized on the surface of mesoporous materials by a number of different methods.
  • catalytically active complexes have been bound to mesoporous supports by condensing alkoxysilanes modified with amine, phosphine, or isonitrile groups to the surface of the mesopores in processes similar to those described for the immobilization of palladium complexes.
  • modified mesoporous silicates such as aluminum-doped silicates or [BF 3 ] ⁇ modified silicates
  • strong niobium-nitrogen bonds can be used anchor amine- containing organometallic complexes to niobium-doped silicate surfaces.
  • One method of fixating active rhodium compounds to the surface of silica supports involved condensing triethylsilane ethyldiphenylphosphines onto mesoporous silica supports.
  • the condensation reaction was accomplished by mixing triethoxysilane ethyldiphenylphosphine with the silica foam support in toluene and heating the mixture to 120°C for ⁇ 12 h. This process afforded the compound 7 (FIG. 5).
  • MCF (BET surface area: 767 m 2 /g, median pore size: 250 A, Pore volume: 2.3 cm 3 /g, elemental analysis: 0.36 wt% C, 0.60 wt% H, 0.32 wt% N) was dried at 5x10 "2 mmHg vacuum at 140°C for 12 hours.
  • silica foam [(S- BINAP)Ru(C 8 H n )(CNC 3 H 6 Si(OC 2 H 5 ) 3 )]BF 4 (1.0 g), toluene (150 mL) and water (0.12 mL) were added. The mixture was heated with stirring in a 95°C oil bath for 12 hours.
  • Methyl 2-acetamidoacrylate by [(SiO 2 )OBF 3 ][(DIOP)Rh(COD)], lib (also see equation 2).
  • Methyl 2-acetamidoacrylate (0.50 g) and [(SiO 2 )OBF 3 ][(DIOP)Rh(COD)] (30 mg) were mixed in hexanes (250 mL) and the mixture was transferred to an autoclave. The reactor and the mixture were purged with argon for 5 min, then with hydrogen for 2 min. The hydrogen pressure was increased to 60 psi with a stirrer rotating speed of 1000 rpm. The progress of the reaction was monitored by chromatography.
  • Methyl 2-acetamidoacrylate by [(SiO 2 )CH 2 CH 2 CH 2 NC]Ru(S-BINAP)Cl 2 , 13.
  • Methyl 2-acetamidoacrylate (0.50 g) and [(SiO 2 )CH 2 CH 2 CH 2 NC]Ru(S-BINAP)Cl 2 (30 mg) were mixed in hexane (250 mL) and the mixture was transferred to an autoclave.
  • the reactor and the mixture were purged with argon for 5 min, then with hydrogen for 2 min.
  • the hydrogen pressure was increased to 140 psi with a stirrer rotating speed of 1000 rpm.
  • the progress of the reaction was monitored by chromatography. After 66 h at 25°C, the reaction was stopped. Conversion of the reaction by GC was 100% and the e.e. value of the product was 22%. Results are shown in Table 3.
  • Methyl 2-acetamidoacrylate by [(S- BINAP)Ru(C 8 H n )(CNC 3 H 6 (SiO 2 )]BF 4 , 15.
  • Methyl 2-acetamidoacrylate 250 mg was dissolved in methanol (250 mL) and the solution was transferred to an autoclave. The reactor and the mixture were purged with argon for 5 min, then with hydrogen for 2 min. The hydrogen pressure was increased to 150 psi with a stirrer speed of 1000 rpm.
  • the increase in H 2 pressure was used to blow in 20 mg of the catalyst ([(S- BINAP)Ru(C 8 H ⁇ )(CNC 3 H 6 (SiO 2 )]BF 4 ) from a holding tube.
  • the progress of the reaction was monitored by chromatography. The reaction reached completion after - 4 h at 60°C and the e.e. value of the product was - 65 %.
  • the reaction mixture was removed and centrifuged under argon to recover the catalyst powder. The yellow powder was then rinsed with methanol, centrifuged, and recovered (all under argon) before being reused.
  • the second reaction run was performed under identical conditions except the mass of all reactants used was halved.
  • Photoacoustic infrared spectra (FIG. 9) of the mesoporous material were taken before the immobilization of the Ru complex (FIG. 9(b)), after the immobilization of the Ru complex (FIG. 9(c)), and after the reactions and rinsing with methanol (FIG. 9(d)).
  • An infrared spectrum of the homogeneous catalyst (FIG. 9(a)) is included for comparison.
  • the isonitrile vibration at - 2100 cm “1 and the naphthal vibrations from BINAP at -700 cm “1 are still present after the reactions, indicating that the catalyst remains immobilized on the silica surface.
  • the homogenous complex [(S-BINAP)Ru(C 8 H n )(CNC 3 H 6 Si(OCH 2 CH 3 ) 3 ]BF 4 was also run under identical conditions, except the total mass of catalyst used was 8 mg, to provide a comparison between the activities of the heterogeneous and homogeneous catalysts.
  • the progress of the reaction was monitored by an in situ infrared probe and the e.e. value of the product was determined by chromatography.
  • the reaction reached completion after - 24 h at 60°C and the e.e. value of the product was - 60%.
  • the dimethylitaconate conversion profile versus time as determined by continuous IR monitoring is shown in FIG. 14.
  • Methyl 2-acetamidoacrylate by [(S- BINAP)Ru(C 8 H n )(HSC 2 H 4 (SiO 2 )]BF 4 .
  • Methyl 2-acetamidoacrylate 250 mg was dissolved in methanol (250 mL) and the solution was transferred to an autoclave. The reactor and the solution were purged with argon for 5 min, then with hydrogen for 2 min. The hydrogen pressure was increased to 150 psi and the stirrer speed was adjusted to 1000 rpm.
  • the increase in H 2 pressure was used to blow in 20 mg of the catalyst ([(S- BINAP)Ru(C 8 H u )(HSC 2 H 4 (SiO 2 )]BF 4 ) from a holding tube.
  • the progress of the reaction was monitored by chromatography.
  • the reaction reached 75% convertion after ⁇ 24 h at 60°C and the e.e. value of the product was - 65 %.
  • the conversion of methyl 2- acetamidoacrylate is plotted against time in FIG. 15.
  • the hydrogen pressure was increase to 60 psi with stirrer rotating speed of 1000 rpm.
  • the progress of the reaction was monitored by a column chromatography. After 18 h, the reaction is stopped and the colorless solution was separated from the orange catalyst. Conversion of the reaction by GC was 100% and the e.e. value of the product is 22%.
  • Methyl( ⁇ -acetylamino) acrylate (0.50 g) and [(SiO 2 )CH 2 CH 2 CH 2 NC]Ru(S-BINAP)Cl (30 mg) was mixed in hexanes (250 mL) and the mixture was transferred to an autoclave.
  • the reactor and the mixture were purged with argon for 5 min then with hydrogen for 2 min.
  • the hydrogen pressure was increase to 140 psi with stirrer rotating speed of 1000 rpm.
  • the progress of the reaction was monitored by a column chromatography. After 66 h, the reaction is stopped. Conversion of the reaction by GC was 100% and the e.e. of 22%.

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Abstract

La présente invention concerne un nouveau système catalytique renfermant des catalyseurs immobilisés sur des compositions mésoporeuses ultralarges, et en particulier des compositions présentant un grand pourcentage de pores de diamètre moyen d'au moins 50 Å environ. Des catalyseurs, tels que des complexes organométalliques, peuvent résider dans ces pores pour produire des réactions catalytiques. Les compositions comprennent des silicates liés de manière covalente à un ligand, qui peut être lié à son tour de manière covalente à un fragment organométallique. Dans le cas de catalyseurs organométalliques asymétriques, le catalyseur est lié à la composition mésoporeuse par l'intermédiaire d'un ligand achiral. Les réactions catalytiques comprennent l'hydrogénation, l'hydroformylation, la carbonylation et les réactions de couplage carbone-carbone telles que les réactions de Heck ou de Suzuki. La présente invention concerne un catalyseur servant à mettre en oeuvre des réactions asymétriques pour obtenir des produits à stéréosélectivités élevées. Elle concerne aussi des catalyseurs immobilisés ioniquement. De plus, on peut utiliser les grandes dimensions de pores de ces compositions dans des réactions de polymérisation, en réglant les dimensions des pores afin d'obtenir une distribution des masses moléculaires particulière. Les compositions poreuses comportent d'autres applications, par exemple comme matières de support en chimie combinatoire.
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EP2258707A1 (fr) * 2009-05-19 2010-12-08 Takasago International Corporation Complexes silyl-arène de ruthénium et leur procédé de production
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CN105602612A (zh) * 2015-10-21 2016-05-25 清华大学 一种利用高温气冷堆对生物原油进行加氢精制的方法
CN110560145A (zh) * 2019-09-18 2019-12-13 昆明理工大学 一种催化分解甲硫醇的Mo-SBA-15介孔分子筛的制备方法
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Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0026890D0 (en) * 2000-11-03 2000-12-20 Ici Plc Catalyst
ITMI20012267A1 (it) * 2001-10-29 2003-04-29 Chemi Spa Preparazione ed uso di un catalizzatore eterogeneo per l'idrogenerazione di un doppio legame di un composto carbonilico b-insaturo
US6733828B2 (en) * 2002-01-29 2004-05-11 Kuei-Jung Chao Method of fabricating nanostructured materials
US6852810B2 (en) * 2002-03-28 2005-02-08 Industrial Technology Research Institute Molecular blended polymer and process for preparing the same
US7589041B2 (en) 2004-04-23 2009-09-15 Massachusetts Institute Of Technology Mesostructured zeolitic materials, and methods of making and using the same
US20060258875A1 (en) * 2005-05-10 2006-11-16 Clementine Reyes Methods for manufacturing supported nanocatalysts and methods for using supported nanocatalysts
WO2006135339A1 (fr) * 2005-06-16 2006-12-21 Agency For Science, Technology And Research Particules de mousse mesocellulaires
US8097229B2 (en) * 2006-01-17 2012-01-17 Headwaters Technology Innovation, Llc Methods for manufacturing functionalized inorganic oxides and polymers incorporating same
US8592336B2 (en) 2006-04-11 2013-11-26 Agency For Science, Technology And Research Catalysts for ring-closing metathesis
EP2010318B1 (fr) 2006-04-11 2014-04-02 Agency for Science, Technology and Research Catalyseurs pour metathese par fermeture de cycle
US20080044324A1 (en) * 2006-08-16 2008-02-21 Agency For Science, Technology And Research Recirculating reactor
NO327431B1 (no) * 2006-09-08 2009-06-29 Yara Int Asa Fremgangsmate og anordning for fangst av platinagruppeelementer
ES2319007B1 (es) * 2006-12-07 2010-02-16 Rive Technology, Inc. Metodos para fabricar materiales zeoliticos mesoestructurados.
JP5551062B2 (ja) * 2007-03-22 2014-07-16 エージェンシー フォー サイエンス，テクノロジー アンド リサーチ シリカ系メソセル発泡体へのクリックケミストリーによる触媒の固定
US7557064B2 (en) * 2007-08-13 2009-07-07 Headwaters Technology Innovation, Llc Methods for making immobilized aryl-containing ligands
US8206498B2 (en) * 2007-10-25 2012-06-26 Rive Technology, Inc. Methods of recovery of pore-forming agents for mesostructured materials
US8524625B2 (en) 2009-01-19 2013-09-03 Rive Technology, Inc. Compositions and methods for improving the hydrothermal stability of mesostructured zeolites by rare earth ion exchange
WO2010083488A2 (fr) 2009-01-19 2010-07-22 Rive Technologies, Inc. Introduction de mésoporosité dans des zéolites de rapport si/ai faible
CN102574878A (zh) 2009-10-16 2012-07-11 陶氏技术投资有限责任公司 气相加氢甲酰化方法
US8685875B2 (en) 2009-10-20 2014-04-01 Rive Technology, Inc. Methods for enhancing the mesoporosity of zeolite-containing materials
WO2012004352A2 (fr) 2010-07-08 2012-01-12 Stichting Voor De Technische Wetenschappen Catalyseur mésoporeux à base de complexe de diphosphine-métal de transition pour l'hydroformylation
WO2012138910A2 (fr) 2011-04-08 2012-10-11 Rive Technology, Inc. Zéolithes à squelette modifié, mésoporeuses
US9376324B2 (en) 2012-01-13 2016-06-28 Rive Technology, Inc. Introduction of mesoporosity into zeolite materials with sequential acid, surfactant, and base treatment
WO2013106816A1 (fr) 2012-01-13 2013-07-18 Rive Technology, Inc. Introduction de mésoporosité dans des zéolites pauvres en silice
US8765660B1 (en) 2013-03-08 2014-07-01 Rive Technology, Inc. Separation of surfactants from polar solids
US9662640B2 (en) 2013-12-27 2017-05-30 Rive Technology, Inc. Introducing mesoporosity into zeolite materials with a modified acid pre-treatment step
US9963349B2 (en) 2014-12-11 2018-05-08 Rive Technology, Inc. Preparation of mesoporous zeolites with reduced processing
US10626019B2 (en) 2014-12-30 2020-04-21 W. R. Grace & Co.-Conn. Methods for preparing zeolites with surfactant-templated mesoporosity and tunable aluminum content
CN106076395B (zh) * 2016-06-06 2019-02-19 昆明理工大学 一种Cu-ZnO-ZrO2-NH2/SBA-15复合催化剂的制备方法及其应用
CN106345458A (zh) * 2016-08-23 2017-01-25 上海师范大学 介孔碳‑二氧化硅复合体负载纳米钯催化剂及其合成方法
CN106345461A (zh) * 2016-08-23 2017-01-25 上海师范大学 大孔径介孔碳/二氧化硅负载金纳米催化剂及其合成方法
CN106345462A (zh) * 2016-08-23 2017-01-25 上海师范大学 一种介孔碳纳米球负载金催化剂及其合成方法与应用
CN106362739A (zh) * 2016-08-23 2017-02-01 上海师范大学 介孔碳‑二氧化硅复合体负载纳米金催化剂及其制备方法
CN108993594A (zh) * 2018-06-25 2018-12-14 中科广化（重庆）新材料研究院有限公司 一种有机配体修饰的sba-15固载铂催化剂及其制备方法与应用
WO2020183932A1 (fr) * 2019-03-11 2020-09-17 日本碍子株式会社 Élément catalyseur et réacteur
CN110560173B (zh) * 2019-09-17 2022-03-04 哈尔滨工业大学 双吡啶酰胺铁负载纳米二氧化硅异相催化剂的制备方法和应用方法
CN110483390B (zh) * 2019-09-17 2023-05-26 哈尔滨工业大学 双吡啶酰胺化合物及其合成方法
CN111498862B (zh) * 2020-04-03 2022-07-01 三峡大学 一种球形sba-15介孔分子筛的制备方法及应用
CN113754798A (zh) * 2020-06-05 2021-12-07 中国石油化工股份有限公司 类球形超大孔介孔材料和聚烯烃催化剂及其制备方法以及烯烃聚合方法
US11607678B1 (en) 2021-08-18 2023-03-21 Saudi Arabian Oil Company Surface supported catalysts with pore size control

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5139985A (en) * 1988-05-31 1992-08-18 Himont Incorporated Components and catalyst for the polymerization olefins
US4937218A (en) * 1988-09-06 1990-06-26 Intevep, S.A. Catalytic system for the hydroconversion of heavy oils
US5145816A (en) 1990-12-10 1992-09-08 Mobil Oil Corporation Method for functionalizing synthetic mesoporous crystalline material
US5200058A (en) 1990-01-25 1993-04-06 Mobil Oil Corp. Catalytic conversion over modified synthetic mesoporous crystalline material
DE59205529D1 (de) 1991-01-25 1996-04-11 Ciba Geigy Ag Silangruppen enthaltende Diphosphine, immobilisierte Diophoshine und deren Verwendung als Hydrierkatalysatoren
EP0496699B1 (fr) 1991-01-25 1995-04-26 Ciba-Geigy Ag Disphosphines contenant des groupes silane, diphosphines immobilisées et leur utilisation comme catalyseurs d'hydrogenation
US5824622A (en) * 1994-01-12 1998-10-20 E. I. Du Pont De Nemours And Company Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process
US5736480A (en) 1994-02-22 1998-04-07 California Institute Of Technology Supported phase chiral sulfonated BINAP catalyst solubilized in alcohol and method of asymmetric hydrogenation
US5712402A (en) 1994-08-22 1998-01-27 Board Of Trustees Operating Michigan State University Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation
US5645891A (en) 1994-11-23 1997-07-08 Battelle Memorial Institute Ceramic porous material and method of making same
US5622684A (en) 1995-06-06 1997-04-22 Board Of Trustees Operating Michigan State University Porous inorganic oxide materials prepared by non-ionic surfactant templating route
DE19533484A1 (de) * 1995-09-12 1997-03-13 Basf Ag Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren
DE19533486A1 (de) * 1995-09-12 1997-03-13 Basf Ag Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren
DE69613587T2 (de) 1995-10-13 2002-04-25 K.U. Leuven Research & Development, Leuven Chiraler fester katalysator, seine erzeugung und seine verwendung zur hesrtellung von praktischen enantiomerenreinen produkten
US5800799A (en) * 1996-05-02 1998-09-01 Board Of Trustees Operating Michigan State University Porous inorganic oxide materials prepared by non-ionic surfactant and fluoride ion
DE19639016A1 (de) 1996-09-23 1998-03-26 Basf Ag Mesoporöses Siliciumdioxid, Verfahren zu seiner Herstellung und seiner Verwendung
US6028025A (en) 1996-10-21 2000-02-22 Massachusetts Institute Of Technology Metalloporphyrin oxidation catalyst covalently coupled to an inorganic surface and method making same
GB9705799D0 (en) 1997-03-20 1997-05-07 Contract Chemicals Limited Catalyst and its use in friedel-crafts alkylation of benzyne using long chain olefins
AU7112198A (en) 1997-04-15 1998-11-11 Massachusetts Institute Of Technology Synthesis and application of vapor grafted porous materials
US5932511A (en) * 1997-05-28 1999-08-03 E. I. Du Pont De Nemours And Company Perfluorinated ion-exchange microcomposite catalysts modified with Lewis acid
US5990318A (en) 1998-03-06 1999-11-23 The Hong Kong Polytechnic University Soluble polyester-supported chiral phosphines

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7094730B2 (en) 2002-10-31 2006-08-22 Delphi Technologies, Inc. Gas treatment device, methods for making and using the same, and a vehicle exhaust system
JP2009533374A (ja) * 2006-04-13 2009-09-17 ワッカー ケミー アクチエンゲゼルシャフト 新規のＲｕ−錯体、その製造及び使用
EP2258707A1 (fr) * 2009-05-19 2010-12-08 Takasago International Corporation Complexes silyl-arène de ruthénium et leur procédé de production
JP2011001343A (ja) * 2009-05-19 2011-01-06 Takasago Internatl Corp 含ケイ素置換基で置換された芳香環を配位子とするルテニウム錯体及びその製造方法
US7880025B2 (en) 2009-05-19 2011-02-01 Takasago International Corporation Ruthenium silyl-arene complex , and method for production thereof
EP2275427A1 (fr) * 2009-07-13 2011-01-19 Takasago International Corporation Complexe de ruthénium-diamine et procédés de production de composants actifs optiquement
US8404879B2 (en) 2009-07-13 2013-03-26 Takasago International Corporation Ruthenium-diamine complex and methods for producing optically active compounds
CN103380108A (zh) * 2011-01-11 2013-10-30 “Ivy药品”有限责任公司 用于均质选择性氧化硫醇基团的钯-铜催化剂
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